Late transition metal catalysts for olefin oligomerizations

ABSTRACT

A series of novel late transition metal catalysts for olefin oligomerization have been invented. The catalysts demonstrate high activity and selectivity for linear α-olefins.

CLAIM FOR PRIORITY

[0001] This application claims priority from U.S. S No. 60/421,359 filedOct. 25, 2002 and U.S. S No. 60/421,486 filed Oct. 25, 2002.

TECHNICAL FIELD

[0002] This document relates to late transition metal catalysts forolefin oligomerizations and to methods for making and using thesecatalysts.

BACKGROUND OF THE INVENTION

[0003] Alpha-olefins, especially those containing 6 to 20 carbon atoms,are important items of commerce. They are used as intermediates in themanufacture of detergents, as monomers (especially in linear low-densitypolyethylene), and as intermediates for many other types of products.Consequently, improved methods of making these compounds are desired.Especially desired, is a process capable of making a range of linearα-olefins such as 1-butene and 1-hexene.

[0004] Most commercially produced α-olefins are made by theoligomerization of ethylene, catalyzed by various types of compounds,see for instance B. Elvers, et al., Ed. Ullmann's Encyclopedia ofIndustrial Chemistry, Vol. A13, VCH Verlagsgesellschaft mbH, Weinheim,1989, p. 243-247 and 275-276, and B. Cornils, et al., Ed., AppliedHomogeneous Catalysis with Organometallic Compounds, A ComprehensiveHandbook, Vol. 1, VCH Verlagsgesellschaft mbH, Weinheim, 1996, p.245-258. The major types of commercially used catalysts arealkylaluminum compounds, certain nickel-phosphine complexes, and atitanium halide with a Lewis acid such as AlCl₃. In all of theseprocesses, significant amounts of branched internal olefins anddiolefins are produced. Since in most instances these are undesirableand often difficult to separate, these byproducts are avoidedcommercially.

SUMMARY

[0005] Invention catalyst systems, suitable for solution- orslurry-phase oligomerization reactions to produce α-olefins, comprise aGroup-8, -9, or -10 transition metal component (catalyst precursor) andan activator. Invention catalyst precursors can be represented by thegeneral formula:

[0006] where M is a Group-8, -9, or -10 transition metal, especially Fe,Co and Ni; N is nitrogen; P is phosphorous; Y is a hydrocarbyl bridge inwhich four or more carbon atoms connect between the nitrogen andphosphorus atoms; R¹, R², R³ and R⁴ are independently hydrocarbylradicals such as C₁-C₄₀ aliphatic radicals, C₃-C₄₀ alicyclic radicals,C₆-C₄₀ aromatic radicals or combinations of these; X is independently ahydride radical, a hydrocarbyl radical, or hydrocarbyl-substitutedorganometalloid radical; or two X's are connected and form a 3 to 50atom metallacycle ring. When Lewis-acid activators such asmethylalumoxane, aluminum alkyls, alkylaluminum alkoxides oralkylaluminum halides that are capable of donating an X ligand, asdescribed above, to the transition metal component are used, or when theionic activator is capable of extracting X, one or more X, which mayoptionally be bridged to one another, may additionally be independentlyselected from a halogen, alkoxide, aryloxide, amide, phosphide or otheranionic ligand, provided that the resulting activated catalyst containsas least one M-H or M-C bond into which an olefin can insert.

DEFINITIONS

[0007] The term “hydrocarbyl radical” is sometimes used interchangeablywith “hydrocarbyl” throughout this document. For purposes of thisdisclosure, “hydrocarbyl radical” encompasses C₁-C₅₀ radicals. Theseradicals can be linear, branched, or cyclic, and when cyclic, aromaticor non-aromatic. Thus, the term “hydrocarbyl radical”, in addition tounsubstituted hydrocarbyl radicals, encompasses substituted hydrocarbylradicals, halocarbyl radicals, and substituted halocarbyl radicals, asthese terms are defined below.

[0008] Substituted hydrocarbyl radicals are radicals in which at leastone hydrogen atom has been substituted with at least one functionalgroup such as NR″₂, OR″, PR″₂, SR″, BR″₂, SiR″₃, GeR″₃ and the like orwhere at least one non-hydrocarbon atom or group has been insertedwithin the hydrocarbyl radical, such as O, S, NR″, PR″, BR″, SiR″₂,GeR″₂, and the like, where R″ is independently a hydrocarbyl orhalocarbyl radical. The functional group can be an organometalloidradical.

[0009] Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen orhalogen-containing group (e.g. F, Cl, Br, I).

[0010] Substituted halocarbyl radicals are radicals in which at leastone hydrocarbyl hydrogen or halogen atom has been substituted with atleast one functional group such as NR″₂, OR″, PR″₂, SR″, BR″₂, SiR″₃,GeR″₃ and the like or where at least one non-carbon atom or group hasbeen inserted within the halocarbyl radical such as O, S, NR″, PR″, BR″,SiR″₂, GeR″₂, and the like where R″ is independently a hydrocarbyl orhalocarbyl radical provided that at least one halogen atom remains onthe original halocarbyl radical. The functional group can be anorganometalloid radical.

[0011] In some embodiments, the hydrocarbyl radical is independentlyselected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl,docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl,octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl,tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl,nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl,tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl,nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl,tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl,nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl,tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl,nonacosynyl, or triacontynyl isomers. For this disclosure, when aradical is listed it indicates that radical type and all other radicalsformed when that radical type is subjected to the substitutions definedabove. Alkyl, alkenyl and alkynyl radicals listed include all isomersincluding where appropriate cyclic isomers, for example, butyl includesn-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (andanalogous substituted cyclopropyls); pentyl includes n-pentyl,cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,and neopentyl (and analogous substituted cyclobutyls and cyclopropyls);butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls).

[0012] The transition metal component can also be described ascomprising at least one ancillary ligand that stabilizes the oxidationstate of the metal. Ancillary ligands serve to enforce the geometryaround the metal center. In this disclosure, ancillary ligands have abackbone that comprises nitrogen and phosphorous bridged to each otherby at least 4 atoms.

[0013] For purposes of this disclosure, oligomers include about 2-75 merunits. A mer is defined as a unit of an oligomer or polymer thatoriginally corresponded to the olefin that was used in thepolymerization reaction. For example, the mer of polyethylene would beethylene.

[0014] Abstractable ligands are ligands that are removed from thecatalyst precursor to activate it. They are sometimes assigned the labelX in this disclosure. X are independently hydride radicals, hydrocarbylradicals, or hydrocarbyl-substituted organometalloid radicals; or twoX's are connected and form a 3-to-50-atom metallacycle ring. WhenLewis-acid activators such as methylalumoxane, aluminum alkyls,alkylaluminum alkoxides or alkylaluminum halides that are capable ofdonating an X ligand, as described above, to the transition metalcomponent are used, or when the ionic activator is capable of extractingX, one or more X, which may optionally be bridged to one another, mayadditionally be independently selected from a halogen, alkoxide,aryloxide, amide, phosphide or other anionic ligand, provided that theresulting activated catalyst contains as least one M-H or M-C connectionin which an olefin can insert.

[0015] In some structures throughout this specification the ligand-metalconnection is drawn with an arrow indicating that the electronsoriginally came from the ligand. At other times, connection is shown bydrawing a solid line. One of ordinary skill in the art recognizes thatthese depictions are interchangeable.

[0016] C₆F₅ is pentafluorophenyl or perfluorophenyl.

[0017] For purposes of this document, the term “comprising” isinterchangeable with “including”.

DETAILED DESCRIPTION

[0018] In one embodiment of this invention, the catalyst precursor canbe represented by the following formula:

[0019] where M, N, P, R¹, R², R³, R⁴ and X are defined above, and R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently hydrogen, fluorine,or C₁-C₂₀ hydrocarbyl radicals. The organic group connecting between Nand P takes the place of Y, the hydrocarbyl bridge.

[0020] In other invention embodiments, R¹ and R² are independentlyC₁-C₁₂ hydrocarbyl radicals, C₁-C₆ hydrocarbyl radicals, or methylradicals. In these or other embodiments, R³ and R⁴ are independentlyC₆-C₂₀ hydrocarbyl radicals, C₆-C₁₂ hydrocarbyl radicals, aromaticradicals, cyclohexyl radicals, or phenyl radicals.

[0021] Specific, invention catalyst precursor examples are illustratedby the following formula where some components are listed in Table 1.For Y, alkylenes are diradicals and include all isomers of bridge length4 or greater, for example, hexylene includes 1,6-hexylene, 2,5-hexylene,2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methyl-1,5-pentylene,1,5-hexylene, 3,6-hexylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4-butylene,4-ethyl-1,4-butylene, and 1,4-hexylene. To illustrate members of thetransition metal component, select any combination listed in Table 1.For example, by choosing the first row components, the transition metalcompound would be1-(N,N-dimethylamino)-4-(P,P-dimethylphosphino)butylene nickeldichloride. By selecting a combination of components from Table 1, anexample would be2-(N,N-dimethlamino)-2′-(P,P-dicyclohexylphosphino)biphenyl nickeldibromide. Any combination of components may be selected.

R¹, R², R³, and R⁴ Y M X¹ and X² Methyl Butylene chloride nickel EthylPentylene bromide iron Propyl Hexylene iodide cobalt Butyl Heptylenemethyl palladium Pentyl Octylene ethyl platinum Hexyl Nonylene propylruthenium Heptyl Decylene butyl osmium Octyl Undecylene pentyl rhodiumNonyl Dodecylene hexyl iridium Decyl Tridecylene heptyl UndecylTetradecylene octyl Dodecyl Pentadecylene nonyl Tridecyl Hexadecylenedecyl Tetradecyl Heptadecylene undecyl Pentadecyl Octadecylene dodecylHexadecyl Nonadecylene tridecyl Heptadecyl Eicosylene tetradecylOctadecyl Heneicosylene pentadecyl Nonadecyl Docosylene hexadecylEicosyl tricosylene heptadecyl Heneicosyl tetracosylene octadecylDocosyl pentacosylene nonadecyl Tricosyl hexacosylene eicosyl Tetracosylheptacosylene heneicosyl Pentacosyl octacosylene docosyl Hexacosylnonacosylene tricosyl Heptacosyl triacontylene tetracosyl Octacosylcyclohexylene pentacosyl Nonacosyl cyclooctylene hexacosyl Triacontylcyclodecylene heptacosyl Ethenyl cyclododecylene octacosyl Propenyl2,2′-biphenyl nonacosyl Butenyl butenylene triacontyl Pentenylpenentylene hydride Hexenyl hexenylene phenyl Heptenyl heptenylenebenzyl Octenyl octenylene phenethyl Nonenyl nonenylene tolyl Decenyldecenylene methoxy Undecenyl undecenylene ethoxy Dodecenyl dodecenylenepropoxy Ethynyl hexynylene butoxy Propynyl heptynylene dimethylaminoButynyl octynylene diethylamino Pentynyl nonynylene methylethylaminoHexynyl decynylene phenoxy Heptynyl undecynylene benzoxy Octynyldodecynylene allyl Nonynyl butadienylene 1,1-dimethyl allyl Decynylpentadienylene 2-carboxymethyl allyl Undecynyl hexadienyleneacetylacetonate Dodecynyl heptadienylene 1,1,1,5,5,5-hexa-fluoroacetylacetonate Phenyl octadienylene 1,1,1-trifluoro-acetylacetonate Benzyl nonadienylene 1,1,1-trifluoro-5,5-di-methylacetylacetonate Phenethyl decadienylene Tolyl undecadienylene bothX¹ and X² Cyclobutyl dodecadienylene catecholate Cyclopentylhexatrienylene 3,5-dibutylcatecholate Cyclohexyl octatrienylene3,6-dibutylcatecholate Cycloheptyl decatrienylene 3,6-dibutyl-4,5-dimethoxycatecholate Cyclooctyl dodecatrienylene 3,6-dibutyl-4,5-dichlorocatecholate Cyclononyl 3,6-dibutyl-4,5- dibromocatecholateCyclodecyl 1,3-propylene Cyclododecyl 1,4-butylene

[0022] R³ and R⁴ can further independently be defined as one of thefollowing substituents:

[0023] where R′ are independently, hydrogen or C₁-C₅₀ hydrocarbylradicals. Additionally, any two adjacent R′ may independently be joinedto form a saturated or unsaturated cyclic structure.

[0024] Y can further be defined as one of the following bridging groups:

[0025] where R′ is as defined above, A is a non-hydrocarbon atom orgroup (i.e. C═O, C═S, O, S, SO₂, NR*, PR*, BR*, SiR*₂, GeR*₂ and thelike where R* is independently a hydrocarbyl or halocarbyl radical), Eis a Group-14 element including carbon, silicon and germanium, x is aninteger from 1 to 4, and y is an integer from 0 to 4.

[0026] Common activators are useful with this invention: alumoxanes,such as methylalumoxane, modified methylalumoxane, ethylalumoxane andthe like; aluminum alkyls such as trimethyl aluminum, triethyl aluminum,triisopropyl aluminum and the like; alkyl aluminum halides such asdiethyl aluminum chloride and the like; and alkylaluminum alkoxides.

[0027] The alumoxane component useful as an activator typically is anoligomeric aluminum compound represented by the general formula(R″—Al—O)_(n), which is a cyclic compound, or R″(R″—Al—O)_(n)AlR″₂,which is a linear compound. In the general alumoxane formula, R″ isindependently a C₁-C₂₀ alkyl radical, for example, methyl, ethyl,propyl, butyl, pentyl, isomers thereof, and the like, and “n” is aninteger from 1-50. Most preferably, R″ is methyl and “n” is at least 4.Methylalumoxane and modified methylalumoxanes are most preferred. Forfurther descriptions see, EP 279586, EP 561476, WO94/10180 and U.S. Pat.Nos. 4,665,208, 4,908,463, 4,924,018, 4,952,540, 4,968,827, 5,041,584,5,103,031, 5,157,137, 5,235,081, 5,248,801, 5,329,032, 5,391,793, and5,416,229.

[0028] The aluminum alkyl component useful as an activator isrepresented by the general formula R″AlZ₂ where R″ is defined above, andeach Z is independently R″ or a different univalent anionic ligand suchas halogen (Cl, Br, I), alkoxide (OR″) and the like. Most preferredaluminum alkyls include triethylaluminum, diethylaluminum chloride,triisobutylaluminum, tri-n-octylaluminum and the like.

[0029] When alumoxane or aluminum alkyl activators are used, thecatalyst-precursor-to-activator molar ratio is from about 1:1000 to10:1; alternatively, 1:500 to 1:1; or 1:300 to 1:10.

[0030] Additionally, discrete ionic activators such as[Me₂PhNH][B(C₆F₅)₄], [Bu₃NH][BF₄], [NH₄][PF₆], [NH₄][SbF₆], [NH₄][AsF₆],[NH₄][B(C₆H₅)₄] or Lewis acidic activators such as B(C₆F₅)₃ or B(C₆H₅)₃can be used, if they are used in conjunction with a compound capable ofalkylating the metal such as an alumoxane or aluminum alkyl. Discreteionic activators provide for an activated catalyst site and a relativelynon-coordinating (or weakly coordinating) anion. Activators of this typeare well known in the literature, see for instance W. Beck., et al.,Chem. Rev., Vol. 88, p. 1405-1421 (1988); S. H. Strauss, Chem. Rev.,Vol. 93, p. 927-942 (1993); U.S. Pat. Nos. 5,198,401, 5,278,119,5,387,568, 5,763,549, 5,807,939, 6,262,202, and WO93/14132, WO99/45042WO01/30785 and WO01/42249.

[0031] Invention catalyst precursors can also be activated withcocatalysts or activators that comprise non-coordinating anionscontaining metalloid-free cyclopentadienide ions. These are described inU.S. Patent Publication 2002/0058765 A1, published on 16 May 2002.

[0032] When a discrete ionic activator is used, thecatalyst-precursor-to-activator molarratio is from 1:10 to 1.2:1; 1:10to 10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1.2:1; 1:5 to 10:1; 1:5 to 2:1;1:5 to 3:1; 1:5 to 5:1.

[0033] The catalyst-precursor-to-alkylating-agent molar ratio is from1:10 to 10:1; 1:10 to 2:1; 1:10 to 25:1; 1:10 to 3:1; 1:10 to 5:1; 1:2to 10:1; 1:2 to 2:1; 1:2 to 25:1; 1:2 to 3:1; 1:2 to 5:1; 1:25 to 10:1;1:25 to 2:1; 1:25 to 25:1; 1:25 to 3:1; 1:25 to 5:1; 1:3 to 10:1; 1:3 to2:1; 1:3 to 25:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 10:1; 1:5 to 2:1; 1:5to 25:1; 1:5 to 3:1; 1:5 to 5:1.

[0034] The catalyst systems of this invention can additionally beprepared by combining in any order, the bidentate ligand:

[0035] where N, P, Y, R¹, R², R³ and R⁴ are as previously defined and aGroup-8, -9, or -10 halide salt which may optionally be coordinated bysolvent (for example NiX₂ or NiX₂.MeOCH₂CH₂OMe where X=Cl, Br or I) inan activator-compound solution (for example methylalumoxane dissolved intoluene). The reactants may be added in any order, or even essentiallysimultaneously.

[0036] Invention catalyst precursor solubility allows for the readypreparation of supported catalysts. To prepare uniform supportedcatalysts, the catalyst precursor should significantly dissolve in thechosen solvent. The term “uniform supported catalyst” means that thecatalyst precursor or the activated catalyst approach uniformdistribution upon the support's accessible surface area, including theinterior pore surfaces of porous supports.

[0037] Invention supported catalyst systems may be prepared by anymethod effective to support other coordination catalyst systems,effective meaning that the catalyst so prepared can be used foroligomerizing olefin in a heterogeneous process. The catalyst precursor,activator, suitable solvent, and support may be added in any order orsimultaneously. In one invention embodiment, the activator, dissolved inan appropriate solvent such as toluene is stirred with the supportmaterial for 1 minute to 10 hours. The total volume of the activationsolution may be greater than the pore volume of the support, but someembodiments limit the total solution volume below that needed to form agel or slurry (about 100-200% of the pore volume). The mixture isoptionally heated to 30-200° C. during this time. The catalyst can beadded to this mixture as a solid, if a suitable solvent is employed inthe previous step, or as a solution. Or alternatively, this mixture canbe filtered, and the resulting solid mixed with a catalyst precursorsolution. Similarly, the mixture may be vacuum dried and mixed with acatalyst precursor solution. The resulting catalyst mixture is thenstirred for 1 minute to 10 hours, and the catalyst is either filteredfrom the solution and vacuum dried, or vacuum or evaporation aloneremoves the solvent.

[0038] In another invention embodiment, the catalyst precursor andactivator are combined in solvent to form a solution. The support isthen added to this solution and the mixture is stirred for 1 minute to10 hours. The total volume of this solution may be greater than the porevolume of the support, but some embodiments limit the total solutionvolume below that needed to form a gel or slurry (about 100-200% porevolume). The residual solvent is then removed under vacuum, typically atambient temperature and over 10-16 hours. But greater or lesser timesare possible.

[0039] The catalyst precursor may also be supported in the absence ofthe activator, in which case the activator is added to the liquid phaseof a slurry process. For example, a solution of catalyst precursor ismixed with a support material for a period of about 1 minute to 10hours. The resulting catalyst precursor mixture is then filtered fromthe solution and dried under vacuum, or vacuum or evaporation aloneremoves the solvent. The total volume of the catalyst precursor solutionmay be greater than the pore volume of the support, but some embodimentslimit the total solution volume below that needed to form a gel orslurry (about 100-200% of the pore volume).

[0040] Additionally, two or more different catalyst precursors may beplaced on the same support using any of the support methods disclosedabove. Likewise, two or more activators may be placed on the samesupport.

[0041] Suitable solid particle supports typically comprise polymeric orrefractory oxide materials. Some embodiments select porous supports(such as for example, talc, inorganic oxides, inorganic chlorides(magnesium chloride)) that have an average particle size greater than 10μm. Some embodiments select inorganic oxide materials as the supportmaterial including Group-2, -3, -4, -5, -13, or -14 metal or metalloidoxides. Some embodiments select the catalyst support materials toinclude silica, alumina, silica-alumina, and their mixtures. Otherinorganic oxides may serve either alone or in combination with thesilica, alumina, or silica-alumina. These are magnesia, titania,zirconia, and the like. Lewis acidic materials such as montmorilloniteand similar clays may also serve as a support. In this case, the supportcan optionally double as the activator component. But additionalactivator may also be used.

[0042] As well know in the art, the support material may be pretreatedby any number of methods. For example, inorganic oxides may be calcined,and/or chemically treated with dehydroxylating agents such as aluminumalkyls and the like.

[0043] Some embodiments select the carrier of invention catalysts tohave a surface area of 10-700 m²/g, or pore volume of 0.1-4.0 cc/g, andaverage particle size from 10-500 μm. But greater or lesser values mayalso be used.

[0044] Invention catalysts may generally be deposited on the support ata loading level of 10-100 micromoles of catalyst precursor per gram ofsolid support; alternately from 20-80 micromoles of catalyst precursorper gram of solid support; or from 40-60 micromoles of catalystprecursor per gram of support. But greater or lesser values may be used.Some embodiments select greater or lesser values, but require that thetotal amount of solid catalyst precursor does not exceed the support'spore volume.

[0045] Additionally, oxidizing agents may be added to the supported orunsupported catalyst as described in WO 01/68725.

[0046] Process

[0047] In the invention oligomerization processes, the processtemperature may be −100° C. to 300° C., −20° C. to 200° C., or 0° C. to150° C. Some embodiments select ethylene oligomerization pressures(gauge) from 0 kPa-35 MPa or 500 kPa-15 MPa.

[0048] The preferred and primary feedstock for the oligomerizationprocess is the α-olefin, ethylene. But other α-olefins, including butnot limited to propylene and 1-butene, may also be used alone orcombined with ethylene.

[0049] Invention oligomerization processes may be run in the presence ofvarious liquids, particularly aprotic organic liquids. The homogeneouscatalyst system, ethylene, α-olefins, and product are soluble in theseliquids. A supported (heterogeneous) catalyst system may also be used,but will form a slurry rather than a solution. Suitable liquids for bothhomo- and heterogeneous catalyst systems, include alkanes, alkenes,cycloalkanes, selected halogenated hydrocarbons, aromatic hydrocarbons,and in some cases, hydrofluorocarbons. Useful solvents specificallyinclude hexane, toluene, cyclohexane, and benzene.

[0050] Also, mixtures of α-olefins containing desirable numbers ofcarbon atoms may be obtained. Factor K from the Schulz-Flory theory (seefor instance B. Elvers, et al., Ed. Ullmann's Encyclopedia of IndustrialChemistry, Vol. A13, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p.243-247 and 275-276) serves as a measure of these α-olefins' molecularweights. From this theory,

K=n(C_(n)+2 olefin)/n(C_(n) olefin)

[0051] where n(C_(n) olefin) is the number of moles of olefin containingn carbon atoms, and n(C_(n)+2 olefin) is the number of moles of olefincontaining n+2 carbon atoms, or in other words the next higher oligomerof C_(n) olefin. From this can be determined the weight (mass) fractionsof the various olefins in the resulting product. The ability to varythis factor provides the ability to choose the then desired olefins.

[0052] Invention-made α-olefins may be further polymerized with otherolefins to form polyolefins, especially linear low-densitypolyethylenes, which are copolymers containing ethylene. They may alsobe homopolymerized. These polymers may be made by a number of knownmethods, such as Ziegler-Natta-type polymerization, metallocenecatalyzed polymerization, and other methods, see for instance WO96/23010, see for instance Angew. Chem., Int. Ed. Engl., vol. 34, p.1143-1170 (1995); European Patent Application, 416,815; and U.S. Pat.No. 5,198,401 for information about metallocene-type catalysts, and J.Boor Jr., Ziegler-Natta Catalysts and Polymerizations, Academic Press,New York, 1979 and G. Allen, et al., Ed., Comprehensive Polymer Science,Vol. 4, Pergamon Press, Oxford, 1989, pp. 1-108, 409-412 and 533-584,for information about Ziegler-Natta-type catalysts, and H. Mark, et al.,Ed., Encyclopedia of Polymer Science and Engineering, Vol. 6, John Wiley& Sons, New York, 1992, p. 383-522, for information about polyethylene.

[0053] Invention-made α-olefins may be converted to alcohols by knownprocesses, these alcohols being useful for a variety of applicationssuch as intermediates for detergents or plasticizers. The α-olefins maybe converted to alcohols by a variety of processes, such as the oxoprocess followed by hydrogenation, or by a modified, single-step oxoprocess (the modified Shell process), see for instance B. Elvers, etal., Ed., Ullmann's Encyclopedia of Chemical Technology, 5th Ed., Vol.A18, VCH Verlagsgesellschaft mbH, Weinheim, 1991, p. 321-327.

[0054] A set of exemplary catalyst precursors is set out below. Theseare by way of example only and are not intended to list every catalystprecursor that is within the scope of the invention.

[0055] Several structures are shown along with their corresponding name.

EXAMPLES

[0056] The following examples are presented to illustrate the discussionabove. Although the examples may be directed toward certain embodimentsof the present invention, they do not limit the invention in anyspecific way. In these examples, certain abbreviations are used tofacilitate the description. These include standard chemicalabbreviations for the elements and certain, commonly acceptedabbreviations, such as: Me=methyl, Ph=phenyl, Cy=cyclohexyl,MAO=methylalumoxane, COD=cyclooctadiene and DME=ethylene glycol dimethylether.

[0057] All preparations were performed under an inert nitrogenatmosphere using standard Schlenk or glovebox techniques, unlessmentioned otherwise. Dry solvents (toluene, diethyl ether, pentane,methylene chloride) were purchased as anhydrous solvents and furtherpurified by passing them down an alumina (Fluka) column. Ethylene(99.9%) was purchased from BOC (Surrey, United Kingdom).2-(N,N-dimethlamino)-2′-(dicyclohexylphosphino)biphenyl and2-(N,N-dimethlamino)-2′-(diphenylphosphino)biphenyl were purchased fromStrem Chemicals, Inc. Tetramethyltin, nickel(II) bromide ethylene glycoldimethylether complex, and dichloro(1,5-cyclooctadiene)palladium(II)were purchased from Aldrich Chemical Company. Deuterated solvents weredried with CaH and vacuum distilled prior to use.

[0058] Some compounds prepared are illustrated below:

[0059] Preparation of2-(N,N-dimethlamino)-2′-(dicyclohexylphosphino)biphenyl Nickel Dibromide(Compound 1).

[0060] CH₂Cl₂ (25 ml) was added to a Schlenk flask containing2-(N,N-dimethlamino)-2′-(dicyclohexylphosphino)biphenyl (2.00 g, 5.10mmol) and (DME)NiBr₂ (1.23 g, 4.0 mmol) in a dry box. A dark bluesolution formed immediately upon mixing. This solution was stirred for20 hours. Then, it was filtered and recrystallized from CH₂Cl₂/pentane.The product was washed three times with an additional 15 ml of pentaneand dried for 1 hour under vacuum. A blue powder was isolated in 49.0%yield. The product was soluble in CH₂Cl₂. ¹H NMR indicates that it isparamagnetic. Anal. Calcd for (C₂₆H₃₆NPBr₂Ni): C, 51.02%; H, 5.94%; N,2.29%; P, 5.06%. Found: C, 50.72%; H, 6.10%; N, 2.12%; P, 5.02%. The IR(cm⁻¹, KBr): 272, ν(Ni—Br). This compound has also been characterized byx-ray crystallography.

[0061] Preparation of2-(N,N-dimethlamino)-2′-(diphenylphosphino)biphenyl Nickel Dibromide(Compound 2)

[0062] CH₂Cl₂ (25 ml) was added to a Schlenk flask containing the2-(N,N-dimethlamino)-2′-(diphenylphosphino)biphenyl (2.00 g, 5.2 mmol)and (DME)NiBr₂ (1.30 g, 4.2 mmol) in a dry box. A green solution formedimmediately upon mixing. This solution was stirred for 20 hours. Then,it was filtered and recrystallized from CH₂Cl₂/pentane. The product waswashed three times with an additional 15 ml of pentane and dried for 1hour under vacuum. A green powder was isolated in 69.3% yield. Theproduct was soluble in CH₂Cl₂. ¹H NMR indicates that it is paramagnetic.Anal. Calcd for (C₂₆H₂₄NPBr₂Ni): C, 52.03%; H, 4.08%; N, 2.33%; P,5.16%. Found: C, 1.20%; H, 4.24%; N, 2.14%; P, 5.29%.

[0063] Preparation of2-(N,N-dimethylamino)-2′-(dicyclohexylphosphino)biphenyl Palladium MethyChloride (Compound 3)

[0064] (COD)PdCl₂ (2.0 g, 7.0 mmol) was mixed with tetramethyltin (1.16ml, 8.4 mmol) in CH₂Cl₂ (50 ml) at room temperature. The mixture wasstirred overnight until the bright yellow color of the precursor hadvanished. The resulting mixture was filtered through Celite yielding apale yellow solution. The solvent was removed from the that solution,leaving behind an off-white solid, (COD)PdClMe, which was washed twicewith diethyl ether and dried under vacuum. A solution of the white(COD)PdClMe complex (0.775 g, 0.0029 mol dissolved in CH₂Cl₂) wasreacted with 2-(N,N-dimethlamino)-2′-(dicyclohexylphosphino)biphenyl(1.78 g, 0.0045 mol). As a result, a light yellow palladium complexformed. ¹H NMR (250 MHz, CD₂Cl₂, δ, ppm): 0.88-2.94 m (22H, 2×C₆H₁₁);1.06 d (3H, PdCH₃, J_(PH)=2.5 Hz); 2.87 s (6H, 2×CH₃); 6.75-7.68 m (8H,2×C₆H₄). Anal. Calcd for (C₂₇H₃₉NPCIPd): C, 58.91%; H, 7.16%; N, 2.55%;P, 5.63%. Found: C, 59.21%; H, 7.31%; N, 2.38%; P, 5.41%.

[0065] Oligomerization Reactions

[0066] Oligomerization reactions were run in 300 mL HastelloyC Parrreactor equipped with a mechanical stirrer. Catalyst (dissolved in 75 mltoluene) was added to the reactor under argon. Ethylene was added to thereactor at 100 psig, and then the reactor was vented to maintain anatmosphere of ethylene. Methylalumoxane solution (Albemarle, 30 wt % intoluene) was then cannulated in to the reactor. This process causedcatalyst activation to be completed in the presence of the monomer.After activation, the ethylene pressure was adjusted to the desiredvalue. It was attempted to maintain the reactor temperature at roomtemperature; but in cases where the exotherm was very large, higherreaction temperatures were reached. After the reaction had run for anhour, the reactor was cooled in an acetone/dry ice bath and vented. Thereaction was quenched with methanol. A sample of the product solutionwas analyzed by GC/MS after adding nonane as an internal standard. Inthe case of supported transition metal compounds, silica-loaded sampleswere prepared by adding a solution of the transition metal complex inmethylene chloride to silica followed by overnight drying of the silicaunder vacuu. MAO was added to the reactor solution prior to adding thesupported transition metal compound. The results of the oligomerizationreactions are tabulated below in Table 2. TABLE 2 OligomerizationExamples Final Rxn Temper- Activity C₂ ature (mol C₂/ Catalyst^(a)(psig) (° C.) mol Ni · hr) Product 1 820 40 226,200 Linear C₄ to C₁₄ (K*= 0.60)^(b) 1 100 30 26,700 Primarily C₄ and C₆ (linear) 1 800 25155,000 Primarily C₄ and C₆ (linear)^(c) 2 800 30 130,000 C₄ 2 100 308095 C₄

[0067] While certain representative embodiments and details have beenshown to illustrate the invention, it will be apparent to skilledartisans that various process and product changes from those currentlydisclosed may be made without departing from this invention's scope. Theappended claims define the invention's scope.

[0068] All cited patents, test procedures, priority documents, and othercited documents are fully incorporated by reference to the extent thatthis material is consistent with this specification and for alljurisdictions in which such incorporation is permitted.

[0069] Certain features of the present invention are described in termsof a set of numerical upper limits and a set of numerical lower limits.This specification discloses all ranges formed by any combination ofthese limits. All combinations of these limits are within the scope ofthe invention unless otherwise indicated.

1. A composition of matter comprising: (a) a Group-8, -9, or -10transition metal, M, excluding palladium; (b) an ancillary ligandcomprising: (i) a terminal amine comprising two independently selectedhydrocarbyl radicals, R¹ and R²; (ii) a terminal phosphine comprisingtwo independently selected hydrocarbyl radicals, R³ and R⁴; and (iii) ahydrocarbyl bridge, Y, comprising a backbone wherein the hydrocarbylbridge connects between the terminal amine and the terminal phosphineand wherein the backbone comprises a chain that is four or more carbonatoms long; and (c) an abstractable ligand, X.
 2. The composition ofmatter of claim 1 with the following formula:

wherein (a) M is a Group-8, -9, or -10 transition metal, excludingpalladium, (b) N is nitrogen; (c) P is phosphorus; (d) R¹, R², R³, andR⁴ are independently hydrocarbyl radicals; (e) Y is a hydrocarbyl bridgecomprising a backbone wherein the backbone comprises a chain that isfour or more carbon atoms long; (f) X is independently an abstractableligand.
 3. The composition of matter of claim 2 wherein R¹, R², R³, andR⁴ are independently selected from C₁-C₄₀ hydrocarbyls.
 4. Thecomposition of matter of claim 3 wherein R¹, R², R³, and R⁴ areindependently selected from C₁-C₃₀ hydrocarbyls.
 5. The composition ofmatter of claim 4 wherein R¹, R², R³, and R⁴ are independently selectedfrom methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl,decynyl, undecynyl, dodecynyl, phenyl, benzyl, phenethyl, tolyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, cyclodecyl, cyclododecyl radicals.
 6. The composition ofmatter of claim 5 wherein R¹, R², R³, and R⁴ are independently selectedfrom from methyl, ethyl, propyl, butyl, cyclohexyl, phenyl, tolyl,benzyl, and phenethyl.
 7. The composition of matter of claim 2 wherein Xare independently hydride radicals; hydrocarbyl radicals;hydrocarbyl-substituted, organometalloid radicals; or two X's areconnected to form a 3-to-50-atom metallacycle ring.
 8. The compositionof matter of claim 2 wherein X are independently halogen, alkoxide,aryloxide, amide, or phosphide radicals.
 9. The composition of matter ofclaim 8 wherein X are independently chloride, bromide, iodide, methoxy,ethoxy, propoxy, butoxy, dimethylamino, diethylamino, methylethylamino,phenoxy, benzoxy,
 10. The composition of matter of claim 7 wherein X areindependently halogen, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, hydride, phenyl, benzyl,phenethyl, tolyl,
 11. The composition of matter of claim 2 wherein X areindependently allyl, 1,1-dimethyl allyl, 2-carboxymethyl allyl,acetylacetonate, 1,1,1,5,5,5-hexa-fluoroacetylacetonate,1,1,1-trifluoro-acetylacetonate, or1,1,1-trifluoro-5,5-di-methylacetylacetonate radicals.
 12. Thecomposition of matter of claim 2 wherein M is selected from nickel,iron, cobalt, platinum, ruthenium, osmium, rhodium, and iridium.
 13. Thecomposition of matter of claim 12 wherein M is selected from iron,nickel, and cobalt.
 14. The composition of matter of claim 12 wherein Yis selected from butylene, pentylene, hexylene, heptylene, octylene,nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene,pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene,eicosylene, heneicosylene, docosylene, tricosylene, tetracosylene,pentacosylene, hexacosylene, heptacosylene, octacosylene, nonacosylene,triacontylene, cyclohexylene, cyclooctylene, cyclodecylene,cyclododecylene, biphenyl, butenylene, penentylene, hexenylene,heptenylene, octenylene, nonenylene, decenylene, undecenylene,dodecenylene, hexynylene, heptynylene, octynylene, nonynylene,decynylene, undecynylene, dodecynylene, butadienylene, pentadienylene,hexadienylene, heptadienylene, octadienylene, nonadienylene,decadienylene, undecadienylene, dodecadienylene, hexatrienylene,octatrienylene, decatrienylene, and dodecatrienylene radicals.
 15. Thecomposition of matter of 14 wherein Y is selected from biphenyl.
 16. Thecomposition of matter of 14 wherein Y has one of the following formulas:

where (a) R′ are independently, hydrogen or C₁-C₅₀ hydrocarbyl radicals;(b) A is a non-hydrocarbon atom functional group; (c) E is a Group-14element; (d) x is an integer from 1 to 4; and (e) y is an integer from 0to
 4. 17. The composition of claim 16 wherein A is selected from C═O,C═S, O, S, SO₂, NR*, PR*, BR*, SiR*₂, and GeR*₂ wherein R* isindependently a hydrocarbyl or halocarbyl radical.
 18. A composition ofmatter comprising the reaction product of an activator and thecomposition of matter of claim
 2. 19. A composition of matter comprisingthe reaction product of (a) the composition of matter of claim 18 and(b) ethylene, propylene, 1-butene, or a mixture of any two or all threeof ethylene, propylene, and 1-butene.
 20. A polymerization methodcomprising the step of providing at least one composition of matter ofclaim
 2. 21. The polymerization method of claim 16 wherein the catalystsactivity exceeds 8000 moles of ethylene per mole transition metal perhour
 22. The polymerization method of any of claim 20 further comprisingrecovering a product comprising greater than 50 wt % of linear C₄-C₁₄α-olefins based on the total weight of polymerized product.
 23. Thepolymerization method of claim 22 wherein the product comprises greaterthan 80 wt % of linear C₄-C₁₄ α-olefins.
 24. The polymerization methodof claim 23 wherein the product comprises greater than 50 wt % of linearC₄ and C₆ α-olefins.
 25. The polymerization method of claim 24 whereinthe product comprises greater than 80 mol % of linear C₄ and C₆α-olefins.
 26. A composition of matter comprising the reaction productof: (a) an activator; and (b) a catalyst precursor with the followingformula:

wherein (i) M is iron, nickel, cobalt, and palladium; (ii) N isnitrogen; (iii) P is phosphorus; (iv) R¹, R², R³, and R⁴ areindependently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, ethenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl,undecenyl, dodecenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, phenyl,benzyl, phenethyl, tolyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl radicals;(v) Y is a hydrocarbyl bridge comprising a backbone wherein the backbonecomprises a chain that is four or more carbon atoms long; (vi) X areindependently abstractable ligands.
 27. A composition of mattercomprising the reaction product of: (a) an activator; and (b) a catalystprecursor with the following formula:

wherein (i) M is from nickel, iron, cobalt, palladium, platinum,ruthenium, osmium, rhodium, and iridium; (ii) N is nitrogen; (iii) P isphosphorus; (iv) R¹, R², R³, and R⁴ are independently selected frommethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl,decynyl, undecynyl, dodecynyl, phenyl, benzyl, phenethyl, tolyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, cyclodecyl, cyclododecyl radicals; (v) Y is a hydrocarbylbridge comprising a backbone wherein the backbone comprises a chain thatis four or more carbon atoms long; and (vi) X are independentlychloride, bromide, iodide, methoxide, ethoxide, dimethylamide,diethylethoxide, phenoxide, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, hydride, phenyl, benzyl,phenethyl, tolyl, methoxy, ethoxy, propoxy, butoxy, dimethylamino,diethylamino, methylethylamino, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di-methylacetylacetonate radicals; or two X's areconnected to form a 3-to-40-atom metallacycle ring.
 28. A composition ofmatter comprising the reaction product of: (a) an activator; and (b) acatalyst precursor with the following formula:

wherein (i) M is from nickel, iron, cobalt, palladium, platinum,ruthenium, osmium, rhodium, and iridium; (ii) N is nitrogen; (iii) P isphosphorus; (iv) R¹, R², R³, and R⁴ are independently selected frommethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl,decynyl, undecynyl, dodecynyl, phenyl, benzyl, phenethyl, tolyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, cyclodecyl, cyclododecyl radicals; (v) Y is is selected frombutylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene,hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosylene,heneicosylene, docosylene, tricosylene, tetracosylene, pentacosylene,hexacosylene, heptacosylene, octacosylene, nonacosylene, triacontylene,cyclohexylene, cyclooctylene, cyclodecylene, cyclododecylene, biphenyl,butenylene, penentylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, hexynylene,heptynylene, octynylene, nonynylene, decynylene, undecynylene,dodecynylene, butadienylene, pentadienylene, hexadienylene,heptadienylene, octadienylene, nonadienylene, decadienylene,undecadienylene, dodecadienylene, hexatrienylene, octatrienylene,decatrienylene, and dodecatrienylene radicals; and (vi) X areindependently chloride, bromide, iodide, methoxide, ethoxide,dimethylamide, diethylethoxide, phenoxide, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl,hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hydride,phenyl, benzyl, phenethyl, tolyl, methoxy, ethoxy, propoxy, butoxy,dimethylamino, diethylamino, methylethylamino, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di-methylacetylacetonate radicals; or two X's areconnected to form a 3-to-40-atom metallacycle ring.
 29. A composition ofmatter comprising the reaction product of: (a) an activator; and (b) acatalyst precursor with the following formula:

wherein (i) M is a Group-8, -9, or -10 transition metal; (ii) N isnitrogen; (iii) P is phosphorus; (iv) R¹, R², R³, and R⁴ R¹, R², R³, andR⁴ are independently hydrocarbyl radicals; (v) Y is represented by oneof the following formulas:

where R′ are independently, hydrogen or C₁-C₅₀ hydrocarbyl radicals; Ais a non-hydrocarbon atom functional group; E is a Group-14 element; xis an integer from 1 to 4; and y is an integer from 0 to
 4. (vi) X areindependently chloride, bromide, iodide, methoxide, ethoxide,dimethylamide, diethylethoxide, phenoxide, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl,hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hydride,phenyl, benzyl, phenethyl, tolyl, methoxy, ethoxy, propoxy, butoxy,dimethylamino, diethylamino, methylethylamino, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di-methylacetylacetonate radicals; or two X's areconnected to form a 3-to-40-atom metallacycle ring.
 30. A polymerizationmethod wherein the catalysts activity exceeds 8000 moles of ethylene permole transition metal per hour comprising the step of providing at leastone composition of matter comprising the reaction product of: (a) anactivator; and (b) a catalyst precursor with the following formula:

wherein (i) M is iron, nickel, cobalt, and palladium; (ii) N isnitrogen; (iii) P is phosphorus; (iv) R¹, R², R³, and R⁴ areindependently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, ethenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl,undecenyl, dodecenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, phenyl,benzyl, phenethyl, tolyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl radicals;(v) Y is a hydrocarbyl bridge comprising a backbone wherein the backbonecomprises a chain that is four or more carbon atoms long; (vi) X areindependently abstractable ligands.
 31. A polymerization method whereinthe catalysts activity exceeds 8000 moles of ethylene per moletransition metal per hour comprising the step of providing at least onecomposition of matter comprising the reaction product of: (a) anactivator; and (b) a catalyst precursor with the following formula:

wherein (i) M is from nickel, iron, cobalt, palladium, platinum,ruthenium, osmium, rhodium, and iridium; (ii) N is nitrogen; (iii) P isphosphorus; (iv) R¹, R², R³, and R⁴ are independently selected frommethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl,decynyl, undecynyl, dodecynyl, phenyl, benzyl, phenethyl, tolyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, cyclodecyl, cyclododecyl radicals; (v) Y is a hydrocarbylbridge comprising a backbone wherein the backbone comprises a chain thatis four or more carbon atoms long; and (vi) X are independentlychloride, bromide, iodide, methoxide, ethoxide, dimethylamide,diethylethoxide, phenoxide, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, hydride, phenyl, benzyl,phenethyl, tolyl, methoxy, ethoxy, propoxy, butoxy, dimethylamino,diethylamino, methylethylamino, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di-methylacetylacetonate radicals; or two X's areconnected to form a 3-to-40-atom metallacycle ring.
 32. A polymerizationmethod wherein the catalysts activity exceeds 8000 moles of ethylene permole transition metal per hour comprising the step of providing at leastone composition of matter comprising the reaction product of: (a) anactivator; and (b) a catalyst precursor with the following formula:

wherein (i) M is from nickel, iron, cobalt, palladium, platinum,ruthenium, osmium, rhodium, and iridium; (ii) N is nitrogen; (iii) P isphosphorus; (iv) R¹, R², R³, and R⁴ are independently selected frommethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl,decynyl, undecynyl, dodecynyl, phenyl, benzyl, phenethyl, tolyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, cyclodecyl, cyclododecyl radicals; (v) Y is is selected frombutylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene,hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosylene,heneicosylene, docosylene, tricosylene, tetracosylene, pentacosylene,hexacosylene, heptacosylene, octacosylene, nonacosylene, triacontylene,cyclohexylene, cyclooctylene, cyclodecylene, cyclododecylene, biphenyl,butenylene, penentylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, hexynylene,heptynylene, octynylene, nonynylene, decynylene, undecynylene,dodecynylene, butadienylene, pentadienylene, hexadienylene,heptadienylene, octadienylene, nonadienylene, decadienylene,undecadienylene, dodecadienylene, hexatrienylene, octatrienylene,decatrienylene, and dodecatrienylene radicals; and (vi) X areindependently chloride, bromide, iodide, methoxide, ethoxide,dimethylamide, diethylethoxide, phenoxide, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl,hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hydride,phenyl, benzyl, phenethyl, tolyl, methoxy, ethoxy, propoxy, butoxy,dimethylamino, diethylamino, methylethylamino, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di-methylacetylacetonate radicals; or two X's areconnected to form a 3-to-40-atom metallacycle ring.
 33. A polymerizationmethod wherein the catalysts activity exceeds 8000 moles of ethylene permole transition metal per hour comprising the step of providing at leastone composition of matter comprising the reaction product of: (a) anactivator; and (b) a catalyst precursor with the following formula:

wherein (i) M is a Group-8, -9, or -10 transition metal; (ii) N isnitrogen; (iii) P is phosphorus; (iv) R¹, R², R³, and R⁴, R¹, R², R³,and R⁴ are independently hydrocarbyl radicals; (v) Y is represented byone of the following formulas:

where R′ are independently, hydrogen or C₁-C₅₀ hydrocarbyl radicals; Ais a non-hydrocarbon atom functional group; E is a Group-14 element; xis an integer from 1 to 4; and y is an integer from 0 to
 4. (vi) X areindependently chloride, bromide, iodide, methoxide, ethoxide,dimethylamide, diethylethoxide, phenoxide, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl,hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hydride,phenyl, benzyl, phenethyl, tolyl, methoxy, ethoxy, propoxy, butoxy,dimethylamino, diethylamino, methylethylamino, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di-methylacetylacetonate radicals; or two X's areconnected to form a 3-to-40-atom metallacycle ring.